Polyepoxide, phenol-aldehyde condensates, mixed ester compositions



United States atent ()flice Z,9fi7,725 Patented Oct. 6, 1959 IPOLYEPOXIDE, PHENOL-ALDEHYDE CONDEN- SATES, ESTER COMPOSITIONS Sylvan 0. Greenlee, Racine, Wis., assignor to S. C. Johnson 8: Son, Inc., Racine, Wis.

No Drawing. Application November 19, 1956 Serial No. 622,766

11 Claims. (c1. 260-19) This invention relates to new products and compositions resulting from the reaction of phenol-aldehyde condensates, polyepoxides, and mixed esters prepared from hydroxyaryl substituted aliphatic acids, modifying organic acids, and polyhydric alcohols, the compositions being valuable in the manufacture of varnishes, molding compositions, adhesives, films, molded articles, etc. Accord ing to the present invention, the phenol-aldehyde conden sates, polyepoxide materials and mixed esters may be reacted in regulated proportions to produce initial reaction mixtures as well as intermediate and final reaction products.

An object of this invention is the production of compositions containing phenol-aldehyde condensates, polyepoxides, and mixed esters of hydroxyaryl-substituted aliphatic acids, modifying organic acids, and polyhydric alcohols in proportions suitable for reaction to form resins, films, coating compositions, etc.

Another object of this invention is the production of intermediate reaction products from initial reaction mixtures of these phenol-aldehyde condensates, polyepoxides, and mixed esters capable of further reaction on the application of heat to form insoluble, infusible products.

Another object of this invention is the production of initial and intermediate reaction mixtures of the hereinbefore described character which are stable at ordinary temperatures for relatively long periods of time yet which may be converted to polymeric products upon the application of heat.

Still another object of this invention is the production of final reaction products from these initial and intermediate reaction mixtures characterized by such physical properties as hardness, flexibility, and toughness, and such chemical properties as resistance to the chemicals and water. These and other objects and advantages are attained by the present invention, various novel features of which will become more fully apparent from the following description with particular reference to specific examples which are to be considered as illustrative only.

In the preparation of polymeric, infusible, and insoluble compositions for use in protective coating films, molding compositions, adhesives, etc., one of the major problems is to obtain a product which possesses the necessary hardness but which still retains the desired flexibility and toughness. widely used in preparing such polymers although a recognized major problem has continued to be a method of plasticizing the compositions.

In this invention it has been found that the polyepoxides reacted with the herein described mixed esters and aldehyde condensates provide a new series of compositions possessing a number of outstanding properties. By the proper selection of the mixed ester and aldehyde condensate such properties as flexibility, hardness, gloss, Water and chemical resistance, and air-drying or heat-converting characteristics can be easily imparted and readily regulated. These characteristics are incorporated into the composition by primary chemical bonding and, therefore,

In the plastics field, polyepoxides have been no problem exists of plasticizer migration or loss through volatilization.

, In general, the epoxides contemplated for use are compounds containing an average of more than 1 up to about 20 epoxide groups per molecule. Such compounds, free from functional groups other than epoxide and hydroxyl, are reacted with active hydrogen-containing groups, such as the hydroxyl groups supplied by the mixed esters herein contemplated. Typical epoxides which have been found to be operable are resinous polyepoxides, resinous polyepoxide-polyesters, epoxidized natural oils, and simple aliphatic polyepoxides.

The mixed esters contemplated for use are those prepared from polyhydric alcohols, modifying organic acids, and hydroxyaryl-substituted aliphatic acids. Variations can be obtained in the mixed ester through judicious selection of the modifying organic acid and polyhydric alcohol.

. proper phenol and aldehyde.

The mixed esters generally are conveniently prepared by esterifying polyhydric alcohols with a mixture of a hydroxyaryl-substituted aliphatic acid and a modifying organic acid under conditions whereby the aryl-hydroxyl groups of the hydroxyaryl-substituted aliphatic acid are substantially unreacted. Since these aryl-hydroxyl groups are more acidic in nature than the alcoholic hydroxyl groups of the polyhydric alcohols, the reaction of aryl-hydroxyl groups will be insignificant in those cases where the reaction mixtures contain about equivalent amounts or more of alcoholic hydroxyl groups for each equivalent of carboxyl groups, and generally it was found that excellent products were obtained using such proportions.

The hydroxyaiyl-substituted aliphatic acid contemplated for use herein should have two hydroxyaryl groups attached to a single carbon atom. The preparation of such an acid is most conveniently carried out by condensing a keto-acid with the desired phenol. Experience in the preparation of bisphenol and related compounds indicates that the carbonyl group of the keto-acid should be positioned next to a terminal methyl group in order to obtain satisfactory yields. Prior applications, Serial Nos. 464,607 and 489,300, filed October 25, 1954, and February 18, 1955, respectively, disclose a number of illustrative compounds suitable for use as the Diphenolic Acid and methods of preparing the same. These materials, which are referred to for convenience as Diphenolic Acid or DPA, consist of the condensation products of levulinic acid and phenol, substituted phenols, or mixtures thereof. It is to be understood that the phenolic nuclei of the Diphenolic Acid may be substituted with any groups which will not interfere with the reactions contemplated herein. For example, the nuclei may be alkylated with alkyl groups of from 1-5 carbon atoms as disclosed in my copending application Serial No. 489,300 or they may be halogenated. The Diphenolic Acid derived from substituted phenols, such as the alkylated phenols, are sometimes more desirable than the products obtained from unsubstituted phenols since the alkyl groups provide better organic solvent solubility, flexibility, andwater resistance. However, the unsubstituted product is usually more readily purified.

Polyhydric alcohols which may be used .in the preparation of the mixed esters include both the resinousand nonresinous-type alcohols. Illustrative of the nonresinous-type of polyhydric alcohols are such materials as ethylene glycol, polyethylene glycols, propylene glycol, polypropylene glycols, 1,4-butanediol, 2,5-pentanediol,

1,6-hexanediol, neopentyl glycol, glycerol, erythritoLj pentaerythritol, polypentaerythritols, sorbitol, manitol,

3 alphamethyl'glucoside, polyallyl alcohols, diethanolamine, triethanolamin'e and tetramethylol "clyclohexanol.

The resinous polyhydric alcohols which may be employed can be illustrated by suchproducts as those prepared by the reaction of phenol-formaldehyde conden sates with chlorohydrins. For example, an alkyl phenol may be condensed with formaldehyde to form an intermediate methylold'erivative and an alkaline solution of this intermediate may then be treated with a chlorohydrin, such as glycerol monochlorohydrin, to yield after condensation'a polymeric polyhydric alcohol. Still other resinous polyhydric alcohols may be illustrated by the alcoholic 'epoxide resins which are polyether derivatives of polyhydric phenols and such polyfunctional materials as polyhalohydrins, polyepoxides, or epihalohydrins. Reaction products may be prepared'which are monomeric or polymeric polyhydric alcohols having aliphatic chains and aromatic nuclei connected to each other by ether linkages andco'ntaining terminal epoxidegroups. Prep-- arations of these epoxide'mat'erials, as well 'assome illustrative examples, are described in U.S. Patents 2,456,408, 2,503,726, 2,615,007, 2,615,008, 2,668,805, 2,668,807 and 2,698,315. Well-known commercial examples of these resins are the 'Epon resins marketed by the Shell Chemical Corporation.

The modifying organic acids employed with the hydroxyaryl substituted aliphatic acids in preparing the mixed esters used in this invention include a wide-variety of 'al'iphaticor aromatic, resinous or nonresinous, shortor 'long chain, saturated or unsaturated materials. The selectionof the modifying acid depends upon the characteristics which are desired in the final polymeric prodacts of this invention.

Self-plasticized compositions, which in addition have air-drying characteristics, maybe prepared by employing as the modifying organic acid the drying oil fatty acids." These acidsnormally contain from about 18 to 22 carbon atomsand-are obtained by the saponification of naturally occurring unsaturated vegetable oils. Other acids may be illustrated by the'fish oil acids and the shorter chained unsaturated acid, undecanoic acid which is a;decomposition product of castor oil acids. Mixed esters prepared from these materialssuitable for-use in this invention are more fully described in. a copending application of Greenlee, 'filed April '11, 1955, having Serial No. 500,696 entitled Mixed Esters. 'Lowmolecular weight unsaturated acids may also be used, if only air-drying or-heat-converting characteristics are desired since the plasticization effect of the low molecular eight materials in insignificant. Examples of such acids are crotonic and sorbic acid.

The'saturated monobasic aliphatic acids may also be used in the production of the mixed esters. Such acids offer a convenient means for regulating the plasticity of the resulting products. Examples of these acids are acetic, decanoic and. stearic acid. 'In general, the longer chain acids,'having more'than about carbon atoms, are the most effective. plasticizers. The long-chainsaturated acids may'be obtained by saponification of the vegetable and,

fish oil acids, the unsaturated acids being first hydrogenated toremove their unsaturation. Longer chain saturated acids may be obtained by the saponification of naturally occurrin'gwaxes or'by chemical synthesisusing the so-calledOxo process.

Mixed esters preparedfrom'resinous acids are advantageously employed'in some instances. For example, rosin acids are generally'used in the preparation of polymeric products to impart hardness, glo'ss,*and other resinouscharacteristics. Mixed esters prepared from such materials as these rosin acids" maybe 'advantageously em I ployed in this-invention. The preparation ofsuch mixed esters ismore fully described in the copending applica. tion of Greenlee entitled Mixed Resin Acid Esters}? Serial-No. 519,279, filed lune 30, 1955. Aromatic acids also are valuable as the modifying-organic acidandmay. be illustrated by such-material s as benzoic acid, butyl.v

benzoic acid, phthalic acid, naphthoic acid, and phenoxy acetic acids. These acids are useful'in 'impar'tinghar'dness, rigidity, and toughness to the polymeric products derived therefrom. The modifying acids used in the preparation of the mixed esters also include the dibasic acids such as succinic acid, azelaic acid, sebacic acid, and longer chain acids such as the 86 carbon acids prepared by dimerizingunsaturated vegetable oil acids. In the preparation "of the mixed esters frompolyhydric alcohols, hydroxyaryl-substituted acids and modifying organic acids, the reactants may be used'in varyingproportions of wide ranges.

The ratio of acid 10 .polyhydric alcohol maybe adjusted so that substantially-equivalent amounts of carboxyl and hydroxyl groups are present in the mixture. Such compositions have been found to be particularly valuable. However, it is recognized that the hydroxyl content of the mixture can be increased greatly so as to be substantially in excess of carboxyl groups, for example in the range of about 5:1. Although such products are of value, it is considered undesirable to increase this ratio since the efiect of the DPA and modifying acid is thereby virtually lost.

'Simil'arly,'the ratio of hydroxyaryl-substituted'acid to the modifying organic acid maybe proportioned within relatively Wide ranges. Remarkable products were obtained, for example, when the ratio of'hydroxyaryl-substituted acid to modifying organic acid ranged from about 1:5'and 5 :1. The particular ratio employed, of course, would depend upon the choice of modifying acid and the modifications desired in the reaction mixtures and polymeric'materials prepared from the mixed esters.

The mixed esters. of this invention are conveniently;prepared by direct heating at temperatures of from -275 C. withprovision for the continuous removal of water produced by the condensation. Sincethe'DiphenolicAcid' and mja'ny'of the'modifying organic acids, as well asthe polyhydricalcohols, have relatively high boiling :points, which are in most cases above 190 C., water'may be removed by permitting it to volatilize during esterification. In the case of the preparation of the esters of more volatile organic acids, it is convenient to use the anhydrides or sometimes the acid chlorides. For example, the preparation of a mixed ester containing the acetate would conveniently be prepared by using acetic anhydride for the esterification. In the preparation of'thehigher esters where high temperature is used, removal of the Water may be facilitated by continuously bubbling through the reaction mixture during esterification-a stream of inert gas, such, as carbon dioxide or. nitrogen. It is also sometimes convenient to facilitate the water removal by carrying out the reaction in a vessel provided with a condenser attached thereto through a water trap. A suflicient amount of a volatile water-insoluble solvent is added in order to obtain reflux at the esterification temperature. The

water is continually removed by'azeotropic distillation,

permitting the solvent to return to the reaction mixture after having'dr'opped' the water in-the water trap.

The order 'ofa'ddition of the various ingredients, Di-

phenolic "Acid, modifying organic acid, and polyhydri'c. alcohol, to eachv other may be varied. It is sometimes advantageous to vary the order of reaction to obtain optiinum results with a particular combination of ingredients used. 'Inthe art of high temperature esterification, it is often desirable to use certain esterification catalysts,

and-these may be used in the preparation of the subject mixed esters. Another variation inthe method of pre paring. the mixed esters is that of using the simplee'sters to prepare the esters of, the, pholyhydric alcohols by alcoholysis. For. example, one might use methyl .oleate in an alcoholysis reactionvwith glycerol to. prepare the ole'ic ester of' glycerol.

employing a mixture of polyhydric alcohols and/or a mixture of modifying acids. Thus, products which include various combinations of such reactants are also considered to be within the scope of the present invention.

Examples I through IX, inclusive, describe the preparation of mixed esters of Diphenolic Acid, modifying organic acids, and polyhydric alcohols. The reactions were carried out in a 3-necked flask provided with a mechanical agitator, thermometer, and a water trap attachment for the condenser. The removal of Water formed during es terification was facilitated by the utilization of azeotropic distillation with a small amount of xylene, the xylene being sufficient to give refluxing at the temperature of esterification. The proportions given areexpressed as parts by weight unless otherwise indicated. Acid value represents the number of milligrams of KOH required to neutralize a l-gram sample. The acid values were determined by direct titration. Softening points were determined by Durrans Mercury Method (Journal of Oil and Color Chemists Association 12, 173175 [1929]).

EXAMPLE I EXAMPLE II A mixture of 51 parts of glycerol, 140 parts of dehydrated castor oil acids and 286 parts of 4,4-bis(4- hydroxyphenyl)pentanoic acid was heated over a period of 30 minutes to 90 C. and to 240 C. over a period of another hour. The reaction mixture was held at 240- 245 C. for a period of 4 /2 hours. 'The resulting product, amounting to 448 parts, had an acid value of 9.5 and a softening point of 65 C.

EXAMPLE III A mixture of 278 parts of Epon resin 1004 and 224 parts of linseed oil acids was heated at 220-224 C. for a period of 1% hours. To this mixture was added 57.2 parts of 4,4-bis(4-hydroxyphenyl)pentanoic acid and the heating continued at 230-240 C. for an additional 2% hours. The resulting product had an acid value of 7 and a softening point of 63 C.

EXAMPLE IV A mixture of 280 parts of dehydrated castor oil acids and 149 parts of pentaerythritol was heated to 235 C. and held at this temperature for a period of 1% hours, at which point 797 parts of 4,4-bis(4-hydroxyphenyl) pentanoic acid was added and the heating continued at 210 C. for 6 /2 hours. The reaction mixture was finally heated to 240 C. over a period of /2 hour during which time the pressure was reduced to 20 millimeters. The resulting product amounted to 1130 parts and had an acidvalue of 7.6 and a softening point of 69 C.

. EXAMPLE V A mixture of 172 parts of 4,4-bis(4-hydroxyphenyl) pentanoic acid and 56 parts of linseed oil acids was heated to 220 C. at which point 30 parts of pentaerythritol were added slowly over a period of 12 minutes and the reaction continued at 21'5225 C. for a period of 6 hours. The pressure was reduced to around 20 millimeters during the latter 18 minutes of the reaction period. The product, amounting to 232 parts had an acid value of 5 and a softening point of 79 C.

EXAMPLE VI A mixture of 280 parts of China-wood oil acids and 150 parts of pentaerythritol was heated at 225 C, until the acid value had reached 6. To this mixture was added 850 parts of 4,4-bis(4-hydroxyphenyl)pentanoic acid and the reaction mixture heated for a period of 2 hours at 210-220 C. The pressure was reduced to 30 millimeters during the last 20 minutes of heating. The resulting product had a softening point of C.

EXAMPLE VII A mixtureof 343 parts of 4,4-bis(4-hydroxyphenyl) pentanoic acid, 227 parts of stearic acid and 68 parts of glycerol was heated for a period of 1 hour at 203- 220 C. and for a period of 4 hours at 220-248 C. to give a product having an acid value of 2.9.

EXAMPLE VIII A mixture of 286 parts of 4,4-bis(4-hydroxyphenyl) pentanoic acid, 280 parts of soyabean oil acids and 68 parts of ethylene glycol was heated for a period of 40 minutes at 225 C. and for an additional period of 5 hours at 225238 C. to give a product having an acid value of 9.5.

EXAMPLE IX A mixture of 286 parts of 4,4-bis(4-hydroxyphenyl) pentanoic acid, 280 parts of China-Wood oil acids and 68 parts of ethylene glycol was heated for a period of 6 hours at 220237 C. to give a product having an acid Value of 2.9.

Illustrative of the epoxide compositions which may be employed in this invention are the complex epoxide resins which are polyether derivatives of polyhydric phenols with such polyfunctional coupling agents as polyhalohydrins, polyepoxides, or epihalohydrins. These compositions may be described as polymeric polyhydric alcohols having alternating aliphatic chains and nuclei connected to each other by ether linkages, containing terminal epoxide groups and free from functional groups other than epoxide and hydroxyl groups. It should be understood that significant amounts of the monomeric reaction products are often present. This would be illustrated by I to III below where n equals zero. Preparation of these epoxide materials as well as illustrative examples are described in US. Patents 2,456,408, 2,503,726, 2,615,007, 2,615,008, 2,668,807, 2,688,805, and 2,698,315. Well-known commercial examples of these resins are the Epon resins marketed by the Shell Chemical Corporation. Illustrative of the preparation of these epoxide resins are the following reactions wherein the difunctional coupling agent is used in varying molar excessive amounts:

Polyhydrie phenol and an epihalohydrin bis(hydroxyphenyl)isopropylidene excess epichlorohydrin Polyhydrlc phenol and a polye'poxlde his(hydroxyphenyl)isopropylldene excess but ylene dioxide t =heat V O\ y /C\ Cg CH3 7L CH3 CH3 2 VII Polyhydric phenol and a pol-yhalohydrin bis(hydroxyphenyl)isoprcpylidene excess alpha-glycerol dichlorohydrin HkJ HCH O ?OHQCHOHCHI1 ()CH2CHCHI aqueous l I I alkali Q G 3 0 H3 76 C 3 0 H3 III As used in the above formulas, it indicates the degree of polymerization-depending 'on the molar ratio of reactants. As can' -be seen from these formulas, the complex-epoxide resins used in this-inventioncontain terminal epoxidegroups and alcoholic 'hydroxyl' groups attached to the aliphatic portions of the resin, the latter being formed by the splitting of epoxide groups in the reaction of the same with phenolic hydroxyl groups. Ultimately, the reaction With the phenolic hydroxyl groups of the polyhydric phenols is=generally accomplished by means of epoxide groups formed from halohydrins by the loss 'ofhydmgenand halogen as shown by the following equation:

OHOHCHzCl Ofi CH +HCl IV Other epoxide compositions Which-may be used 'include the polyepoxide'polyesters which may be prepared by esterifying tetrahydrophthalicanhydride with a glycol and epoxidizing the product of the esterification reaction. In the preparation of the polyesters, tetrahydrophthal-ic acid may-also be' used as w'ell as the simpleesters of tetrahydrophthalic-acidsuch as'di'methyI and-'diethyl esters. There is-a tendency with tertiary glycols for'dehydration to occur under the conditionsused for esterification so that'gen'era'lly the primary'and secondary glycols arethe most satisfactory'in'the polyester'formation. Glycols which-may be used in the preparation of this polyester compositioncomprise, in general, those glycols having tWo hydroxylgroups attached to separate carbon atoms "and freefrom functional groups which would' interfere with the esterification "or epoxidation reactions. These glycolsinclude such glycols as' ethylene glycol, diethylene glycol, triethylene glycol, tetramethylene glycol, *propylene glycol, 1 polyethylene glycol, neopentyl glycol, and heXamet-hylene glycol. 'Polyepoxide 'polyesters may be prepared from these polyesters by epoxidizing the unsaturated portions of the tetrahydrophthalic acidresidues in' the-polyester composition. By properly proportioning reaotants in the polyester formation and regulating the 'epoxidation reaction,- polyepoxides having up to 12 or more e'poxide groupsper molecule may be readily prepared. These polyepoxide-polyester" compositions, as well as their preparation, are more fully described in a copending application having Serial No.

503,323, filed April 22, 1955.

Polyepoxidecompositions'useful in this invention also include the epoxidized unsaturated natural oil acid esters, including the unsaturated'vegetable, animal, and fis'h oil acid esters made by reacting these materials with various oxidizing agents. These unsaturated oil acid estersare long chain aliphatic acid esters containing from about 15 to 22 carbon atoms. These acids may be esterified by simple monohydric alcohols such as methyl, ethyl,

or decyl alcohol, by polyhydric alcohols such as glycerol, pentaerythritol,ip'olyal-lyl alcohol, or resinous polyhydric alcohols. -Also suitable are the mixed esters of. polycarboxylic acids and long chain unsaturated'natural oil acids with polyhydric alcohols, such as.glycerol and-pentaerythritol. These epoxidized oil acid esters 'mayeconq tainfrom-more than 1-up to 20 .epoxide :groupsirper molecule. The method of epoxidizing these unsaturated oil acid esters consists of treating them with various oxidizing agents, such as the organic peroxides and the peroxy acids, or with one of the various forms of hydrogen peroxide. A typicalprocedure practiced in the art consists of using hydrogen peroxide in the presence of an organic acid, such asacetic acid and'a'ca'talytic material, such as sulfuricacid. Morereceii'tly epoiridat'ion methods have consisted'of replacingthefiiiineral acid catalyst with a su'lforiated' cation exchange material, such as the sulfonated copolymer of styrene di'vinylbem zene.

The epoxide compositions which may be used'in pre paring the compositions of this invention also include the simple aliphatic polyepoxides'which may be illustrated by the products obtained by polymerizing allyl glycidyl ether through'its unsaturated" portion.

The reaction may be carried to give higher poly'mers than the dimer. Other aliphatic polyepoxidesmsefu l in this invention may be illustrated'by the -poly(epoxyalkyl) ethers derived from polyhydric alcohols. These materials may, in general, be prepared-by reacting an aliphatic polyhydric alcohol with an epihalohydrin in the presence of a suitable catalyst and in turn dehydrohalogenating the product to produce the epoxide composition. The production of these epoxides may be il-lustrated by the reaction of glycerol with epichlorohydrin in the presence of boron trifluoride followed 'by .dehydrohalogenation with sodium aluminate as follows: SE20]?! 0 l BF o-rron 3c EQJH'GH2Ol onion onzoomonorrcmci .onloonzonom o NaAlO: orrocnlcnoncmci CHOCHQCHCIL 0 GHzOCHzCHOHOHzCl CHzOCHaCHCH, v

It is to lie understood that such reactions do not give pure compounds and that the halohydrins formed and the epoxides derived therefrom are of somewhat varied character depending upon the particular reactants, their proportions, reaction time and temperature. In addition to epoxide groups, the epoxide compositions may be characterized by the presence of hydroxyl groups and halogens. Dehydrohalogenation afiects only those hydroxyl groups and halogens which are attached to adjacent carbon atoms. Some halogens may not be re moved in this step in the event that the proximate carbinol group has been destroyed by reaction with an epoxide group. These halogens are relatively unreactive and are not to be considered as functional groups in the conversion of the reaction mixtures of this invention. The preparation of a large number of these mixed polyepoxides is described in the Zech patents, US. 2,538,072, 2,581,464, and 2,712,000. Still other polyepoxides which have been found to be valuable are such epoxide compositions as diepoxy butane, diglycid ether, and epoxidized polybutadiene.

Immediately following is a description of preparations of polyepoxides which will be used to prepare the poly meric compositions of this invention.

The complex resinous polyepoxides used in the examples and illustrative of the commercially prepared products of this type are the Epon resins marketed by Shell Chemical Corporation. The following table gives the properties of some Epon resins which are prepared by the condensation in the presence of alkali of bis(4- hydroxyphenyl)isopropylidene with a molar excess of epichlorohydrin in varying amounts.

1 Based on 40% nonvolatile in butyl carbitol at 25 0.

Examples X through XVI describe the preparation of typical polyepoxide polyesters.

EXAMPLE X Preparation of polyester from tetrahydrophthalic anhydride and ethylene glycol In a 3-necked flask provided with a thermometer, mechanical agitator, and a reflux condenser attached through a water trap was placed a mixture of 3 mols of tetrahydrophthalic anhydride and 2 mols of n-butanol. After melting the tetrahydrophthalic anhydride in the presence of the butanol, 2 mols of ethylene glycol were added. The reaction mixture was gradually heated with agitation to 225 C. at which point a suflicient amount of Xylene was added to give refluxing at esterification temperature. The reaction mixture was then heated with continuous agitation at 225235' C. until an acid value of 4.2 was obtained. This product gave an iodine value of 128.

Epoxidation 0f the polyester resin In a 3-necked flask provided with a thermometer, a mechanical agitator, and a reflux condenser was placed 107 parts of the dehydrated acid form of a cation exchange resin (Dowex 50X-8, 50-100 mesh, Dow Chemical Company, a sulfonated styrene-divinylbenzene copolymer containing about 8% divinylbenzene, the percent divinylbenzene serving to control the amount of crosslinkage. The Dowex resins are discussed in publications entitled Ion Exchange Resins No. 1 and Ion Exchange Resins No. 2, copyright 1954 by Dow Chemical Company, the publications having form number Sp32-254 and Sp31-354, respectively), and 30 parts glacial acetic acid. The mixture of cation exchange resin and acetic acid was allowed to stand until the resin had completely taken up the acid. To this mixture was added 200 parts of the polyester resin dissolved in an equal weight of xylene. To the continuously agitated reaction mixture was added dropwise over a period of 45 minutes to 1 hour, 75 parts of 50% hydrogen peroxide. The reaction temperature was held at 60 C. fquiring the application of some external heat. (In some preparations involving other polyester resins, sufficient exothermic heat is produced during the addition of hydrogen peroxide so that no external heat is required, or even some external cooling may be required.) The reaction was continued at 60 C. until a milliliter sample of the reaction mixture analyzed less than 1 milliliter of 0.1 N sodium thiosulfate in an iodometric determination of hydrogen peroxide. The product was then filtered, finally pressing the cation exchange resin filter cake. The acid value of the total resin solution was 42. The percent nonvolatile of this solution amounting to 400 parts was 50. This 400 parts of solution was thoroughly mixed with parts of the dehydrated basic form of Dowex 1 (an anion exchange resin of the quaternary ammonium type. Dowex 1 isa styrene-divinylbenzene copolymer illustrated by the formula RR N' OH- where R represents the styrene-divinylbenzene matrix and R is a methyl group, manufactured by the Dow Chemical Company). The resulting mixture was then filtered followed by pressing as much of the solution as possible from the anion exchange resin cake. This product had an acid value of 4.5 and an epoxide equivalent of 288 based on a nonvolatile resin content of 42.0%. The epoxide values as discussed herein were determined by refluxing for 30 minutes a 2-gram sample with 50 milliliters of pyridine hydrochloride in excess pyridine. (The pyridine hydrochloride solution was prepared by adding 20 milliliters of concentrated HCl to a liter of pyridine.) After cooling to room temperature, the sample is then back-titrated with standard alcoholic sodium hydroxide.

EXAMPLE XI Following the procedure of Example X a polyester resin was prepared from 5 mols of tetrahydrophthalic anhydride, 4 mols of diethylene glycol, and 2 mols of nbutanol. This product had an acid value of 5.3 and an iodine value of 107. This polyester resin was epoxidized in the manner previously described to give an epoxide equivalent weight of 371 on the nonvolatile content. The nonvolatile content of this resin solution as prepared was 40.2%.

EXAMPLE XII The process of Example X was followed to obtain a polyester resin from 1.1 mols of tetrahydrophthalic anhydride, 1 mol of 1,4-butanediol, and 0.2 mol of n-butanol. The product had an acid value of 8.6. This polyester resin was epoxidized in the same manner to give an epoxide equivalent weight of 292 and an acid value of 5.2 on the nonvolatile content. The nonvolatile content of this resin solution was 41.9%.

Examples XIII and XIV describe the preparation of epoxidized vegetable oil acid esters.

EXAMPLE XIII Epoxidized soybean oil acid modified alkyd resin a. Preparation of alkyd resin.To a kettle provided with a condenser was added 290 parts of white refined soyabean oil. While bubbling a continuous stream of nitrogen through this oil the temperature was raised to 250 C., at which temperature 0.23 part of litharge was added and the temperature held at 250 C. for 5 minutes. While holding the temperature above 218 C., 68 parts of technical pentaerythritol were added after which the temperature was raised to 238 C. and held until a mixture of 1 part of the product and 2 /2 parts of methyl alcohol showed no insolubility (about 15 minutes). At this point 136 parts of phthalic anhydride were added and the temperature gradually raised to 250 C. and held at this temperature for 30 minutes. At this point the condenser was removed from the kettle and the pressure reduced somewhat by attaching to a water aspirator evacuatingglycerol and 828 parts of epichlorohydrin.

system. With continuous: agitation the mixture was held at 250 C. until the acidvalue had reached 10.5. f At this point-theresin was thinned with Xylene to a 48% nonvolatile con-tent having a viscosity of H (Gardner bubble viscosimeter).

'b. Epoxidation of a soybean o il acid modified alkyd resinama 3-necked flask-provided with a thermometer, a'mechanic'al agitator and a reflux condenser'was placed 70parts of dehydrated acid form of a cation exchange resin (Dowex 50X.8 and15- parts of glacial'acetic acid. The mixture of cation exchange resin and acetic acid wasv allowed to; stand until the resin had completely taken up the acid. To this mixture was. added 3-15 parts of thealkyd resin solution described in the above paragraph and 190 partsof xylene. To the continuously agitated reaction mixture was added dropwise 38 parts of 50% hydrogen-peroxide. The reaction temperature was held at 60 C. until amilliliter sample of thereaction mixture analyzed less than one milliliter of 0.1 N sodium thiosulfate in an iodometric determination of hydrogen peroxide. The product was then filtered, finally pressing the "cationexchange resin filter cake. The epoxide equivalent onthe' nonvolatile content was 475. w In order to remove the free acidity from the epoxidized product, 400 parts of the solution 'wer'etho'roughly' mixed with T parts of the dehydrated basic form of Dowex l (an amine type 'anionexchangeresin). The resultingrnixturewas then filtered, followed by pressing as much'of the solution-as possible from the ani'onexchange'resin cake.

EXAMPLE XIV Ep'oxidized soybeanoil -A'dr nex 710, an epoxidized soyabea'n oil having an equivalent weight to an epoxide of 263, was dissolvedin methyl ethyl ketone to a nonvolatile content "of 59%. Admex 710, a product of the Archer-Danicls-Midland Company, has an acid value of 1, a viscosity of 3.3 stokes at 25 C.-and an average molecular-weight 015937.

'Examples XV and XVI describe the 'preparati'o'n'of simple aliphatic polyepoxides.

EXAMPLE XV In a reaction vessel provided with a mechanical stirrer and external cooling means was placed 276 parts 'of To this reaction mixture was added 1 part of 45% boron'trifluoride ether solution diluted with) parts of ether.- The reaction mixture'was agitated continuously. The temperature rose to 50 C. over a period of 1' hour and 45 minutes at which time-external cooling with ice water was'applied. The temperature was held between 50 and 75 C. for 1 hour and 20 minutes. To 370 parts of this productin"a"re action vessel provided with a mechanical agitator and a reflu'x condenser was added 900 parts of dioxane and 300 parts of powdered sodium aluminate. With continuous agitation this reaction mixture was gradually heated to 92 C. over a period'of 1 hour and 50 minutes, and held at this temperature for '8 hours and 50 minutes. Aftercooling to room temperature, an inorganic material was removed by filtration. The dioxane and low boiling products were removed by heating the filtrate to 205 C. at "20 mm. pressure to give a pale yellow product. The p'ox'ide equivalent of this product was determined by treating a 1 gram sample with an excess of pyridine containing pyridine'hydrochloride (made by adding 20 of'concentrated hydrochloric acid per liter of pyridine) atthe boiling point for 20 minutes and back-titratin the excess pyridin'e hydrochloride with 0.1 N sodium hydroxide usingphenolp'hthalein asindicator and considering one HCl as equivalentto one epoxide group. The epexrde equivalent on this product was found t'obe 152'.

EXAMPLE XVI brad-necked flask provided with a thermometer,.-a mechanical-agitatonva reflux condenser and a dropping funnel was. placed 402-parts of allylglycidyl ether. With continuous agitation the temperature was raised to C. at which time one part of a solution of methylethyl ketone peroxide dissolved in die'thyl phthalate to"a'f6 l%' content was added. The temperature was 'held at 160* C. for a period of 8 hours, adding one-part ofthe methyl ethyl ketone peroxide solution each 5 minutes during this 8-hour period. After the reaction mixture had stood overnight, the volatile ingredients were removed by vacuum distillation. The distillation was Senec 19 mmrpressure and a pot temperature of 26 (land volatile material finally removed at a pressure of 3 and a pot temperature of 50 C. The residual product had a molecular weight of 418 and equivalent weight to epoxide content of 198, the yield amounting to 250 'parts.

The phenol-aldehyde condensates used in making the compositions herein described are those form'edby the reaction of aldehydes and phenols which contain reactive phenolic hydroxyl groups. Phenol and formaldehydere. act to form a variety of reactionpro'ducts depending. upon the proportions and conditions of reaction. Theseinclude products such as phenol 'alcohols, having both phenolic and alcoholic hydroxylgroups, and products of: diphenolmethane type containing phenolic' 'nydrexyr groups. Thecondensation of phenol and formaldehyde canbe carried out with the use of acid or alkaline-condensing agents, and in some cases, by'first'combining the aldehyde with an alkali, such as ammonia to form hexamethylenetetramine, and reacting the latter with the phenol. The phenol-aldehyde resins at an initial or intermediate stage of reaction are intended to be included in the term phenol-aldehyde condensates as used herein.

In general, the phenol-aldehyde condensates should not have their condensation carried so far as to become insoluble and nonreactive. It is preferred in the preparation of'the instant composition that they be used at an intermediate stage or at a stage of reaction such that they contain reactive'phenolic hydroxyl groups-or both phenoli c and alcoholic hydroxyl groups. This is desirable in order to permit a proper blending of the phenol-aldehydecondensate with the polyepoxide and mixed ester for subsequent reaction therewith.

The phenol-aldehyde condensates may be derived from mononuclear phenols, polynuclear'phenols, monohydric phenols, or polyhydric phenols. The critical requirement for the condensate is that it becompatible with the polyepoxides and mixed ester or with the t'Woreactants in a solventused as a'reaction medium. The phenol-aldehyde condensate, which is essentially the polymethylol phenol rather than a polymer, may be used in' the preparation of the products of this invention, or it may be used after further condensation, in which case some of the methylol groups are considered to have disappeared in the process of condensation. Various so called phenolic resins which result from the reaction of phenols and aldehydes, and particularly from common phenols or-cresols and formaldehyde, are available as commercial products, both of initial and "intermediate character. Such products include resins which are read ily' soluble in common solvents or readily fusible 'so that they can be admixed with the epoxides and mixed esters. and reacted therewith to form-the products of this invention.

In selecting the phenol-aldehyde condensates, one may choose either the heat-converting or the permanentlyfusible type. For example, the formaldehyde reaction products of such phenols as carbol'ic acid, resorcinol, and

bis( 4-hydroxyphenyl)isopropylidene readily convert to infusible, insoluble compositions on the application of. heat. On the'other hand, some of the para-alkylated phenols, as illustrated by p-tert-butylphe'nol, produce permanently fusible resins on the reaction with formaldehyde. Even though fusible condensates are employed, however, insoluble, infusible products result when they are heated incombi-nation with-the epoxides and the mixed esters herein described.

EXAMPLE XVII Condensation of Bisphenol Ibis(para-hydroxyphenyl)isopropylidene] with formaldehyde In a 3-liter 3-necked flask provided with a mechanical agitator, a thermometer, and a reflux condenser was placed 912 parts of Bisphenol A, 960 parts of 37% aqueous formaldehyde, and 2.3 parts of oxalic acid. With continuous agitation the reaction mixture was heated to the reflux temperature and refluxing continued for a period of 1 hour. After permitting the reaction mixture to cool to around 50 C., the water layer was removed by decantation. The phenol-formaldehyde layer was then washed three times with water, which in each case was removed by decantation. The last portion of water was removed by distillation at reduced pressure using a Water aspirator system which gave pressure around 30 40 mm. The temperature during the removal of this last portion of water ranged from 70-90" C. The product, amounting to 1065 parts, was a clear, heavy, syrupy material.

EXAMPLE XVIII Reaction of ptertiary butylphenol with formaldehyde The procedure of preparation, including the dehydration step, was the same as that used in Example XVII. A mixture of 1000 parts of p-tert-butylphenol, 1067 parts of 37% aqueous formaldehyde, and parts of sodium hydroxide was used to give a final yield of 1470 parts of a clear, almost colorless syrupy product.

EXAMPLE XIX Again a reaction procedure, including the dehydration step, was the same as that used in Example XVII. A mixture of 658 parts of phenol, 1400 parts of 37% aqueous formaldehyde, and 6.6 parts of sodium hydroxide was used to give a yield of 1168 parts of a clear, syrupy product.

The polymeric reaction product of epoxides, phenolaldehyde condensates, and mixed esters is eifected by heating a mixture of the same at elevated temperatures, usually in the range of about 100-200 C., the addition of a catalyst ordinarily being unnecessary. However, in some cases it may be desirable to use small amounts of catalyst, such as the boron trifluoride adducts, sodium phenoxides, and sodium alcoholates, as well as the sodium salts of phenol-aldehyde condensates.

The mixture of epoxides, phenol-aldehyde condensates, and mixed esters is of utility at initial or varying intermediate stages of reaction. Thus initial or intermediate reaction products which are soluble in common solvents may be blended in solution in proper concentration and the solution then used as a coating or impregnant for fabrics or paper or for the formation of protective coating films. Heat may be then applied to remove the solvent and bring about polymerization to the insoluble, infusible state. In certain other instances, as for molding compositions, the initial mixture or intermediate reaction product of the three reactants described may be used without a solvent, giving directly a composite which, on the application of heat, converts to a final infusible product.

The reaction mixtures and final reaction products of this invention may be prepared by using varying proportions of mixed ester, epoxide, and phenol-aldehyde condensate. For instance, if relatively flexible final conversion products are desired, they may be advantageously prepared by using an excess of a relatively soft linear epoxide with lesser amounts of a relatively hard aldehyde condensate or by employing an excess of a predominantly linear soft aldehyde condensate with lesser amounts of the harder complex epoxide resins. Con- 14 versely, a harder conversion product could be prepared by using an excess of a relatively hard complex epoxide resin with lesser amounts of the softer aldehyde condensate or by using an excess of relatively hard aldehyde condensates with lesser amounts of the softer linear epoxide resins. Similarly, the amounts of mixed ester used may be adjusted to produce variations in hardness of the final conversion products.

It is apparent, therefore, that a wide range of proportions of the reactants are operable in the herein described compositions depending largely on the desired characteristics of the final product. For example, if an alkali-sensitive coating is desired, a slight excess of acid could be used in preparing the mixed ester, or for certain other applications, itmay be desirable to use a larger amount of polyepoxide to increase the chemical resist ance. In still other instances, flexibility may be increased in a given composition by employing a mixed ester which contains a relatively large amount of a long chain organic acid. Alternatively, flexibility, as well as toughness, may be imparted by larger amounts of a predominantly linear phenol-aldehyde condensate, such as the condensate prepared from p-tert-butylphenol and form aldehyde. In general, while a large excess of the polyepoxide or mixed ester may be applicable for specific applications, most often equivalent or :near equivalent ratios of polyepoxide and mixed ester are employed. The

2:1 to 1:2 ratios have been found to give the best overall characteristics and are therefore preferred, although ratios as high as 1:8 and 8:1 may be used. Equivalents as expressed refer to the weight of the polyepoxide per epoxide group, in the instance of the polyepoxides, and the weight of the ester per hydroxyl group, in the instance of the mixed ester. The phenol-aldehyde condensates are employed to make up from 5-85 of the composition by weight, but it is usually sufiicient to use about 10% on a weight basis.

For the preparation of a composition such as a semiliquid adhesive, it is advantageous to use syrupy phenolaldehyde condensates, which are essentially uncondensed methylol phenols, a relatively low melting polyepoxide and a mixed ester having a softening point (Durrans Mercury Method) below about C. For various applications where solid or very viscous compositions are desired, partially polymerized mixtures could be advantageously used.

In making the new composition and products herein described, the polyepoxides, phenol-aldehyde condensates, and mixed esters may be used in regulated proportions without the addition of other materials. However, other constituents can be admixed with the new compositions, such as filling and compounding materials, plasticizers, pigments, etc. For compositions which tend to give somewhat brittle products on heat c'onversionto the insoluble, infusible state, plasticizers may be added. However, in most instances, it is possible to regulate the proportions of the three reacting ingredients so as to obtain products of suitable flexibility, obviating the necessity for plasticizers. The method of blending the added materials is dependent upon the nature of the materials, such as their softening point and their solubility in common solvents.

The present invention provides a wide range of reaction compositions and products, including initial mixtures of the aforesaid epoxides, phenohaldehyde condensates and mixed esters, their partial or intermediate reaction products, and compositions containing such intermediate reaction products as well as final reaction products. In general, the initial mixtures, as well as the intermediate reaction products, unless too highly polymerized, are soluble in organic solvents used in lacquers, such as ketone and ester solvents. r

In addition to having outstanding physical properties, such as hardness, toughness, and flexibility, the final infusible,.insoluble products have outstanding chemical 15 properties, such as high resistance to oxidation, water, alkali, acids, and organic solvents. It has been observed that the finalconversion'products possess unusually good adhesion to most surfaces, including metal, glass, wood,

'16 tions, it seems probable that conversion to the final polymeric products, 'by reaction between the three reactants described, "involves directpolyme'rization of the epoxide groups inter se, phenol-aldehyde condensatienandreacand plastics. It is this physical property of outstanding tion of epoxide groups with active hydrogen-containing adhesion to a wide variety of surfaces which gives the groups such as methylol hydroxyl. groups and phenolic subject productshigh potential value for use in formulathydroxyl groups, all of which take place to some extent ing adhesives. The superior adhesion to surfaces is also imultaneously "in forming the final products. of extreme value in formulating protective coating films Examples XXthrough LXXVHL in'clusive,illustrate for use on many types of surfaces. The adhesion charthe conversion of combinations {of the polyepoX-ides, acteristics are probably due to the fact that even in the phenol-aldehydecondensates,--and mixed e'sters'to insoluconverted, infusible state, the compositions contain a ble protective coating films. For these preparations, the high percentage of highly polar groups, such as alcoholic polyepoxides, phenol-aldehyde condensates, and-mixed hydroxyl :groups, ether groups, and phenolic hydroxyl esters were cut in a-suitable solvent, the percent nongroups. Despite the high percentage of polar groups in volatile being -4060%. Ihecomplex pol'y'epoxidesand the insoluble, infusible products of this invention, tolersimple aliphatic polyepoxides were dissolved in methyl ance for water is unusually low, apparently due to the ethyl ketone,'- while-the epoxidized-polyesters-and epoxihigh molecular weight and the rigid crosslinked structure dized natural oils were *dissolv'ed'in Xylene. The mixed of the final composition. esters Were'dissolved in methyl ethyl ketone, arid the The polymerizationof mixtures of epoxide, phenolphenol aldehyde condensates-'were c'ut in a mixture of aldehyde condensate, and mixed esters may involve sevbutanol and methylethyl ketone. Thesolutibhs the oral chemical reactions. It willbe appreciated that such polyepoxid'es, phenol-aldehyde condensates, and mixed reactions are very complex and the extent to which each esters were admixed and spreadon-panels in -tl:iin-'-filn1s takes place will y t the p ture, the time of of-i002" wetthickness andbaked for periods 05 50 90 heat treatment,and with the nature of the three reactants minutes at l75-200 C. Proportions hereinafter-"exemployed. While it is not intended to be limited by-any pressed refer to parts"by-weight -and are based on the theoretical explanation of the exact nature of these reacnonvolatile content of the solution of reactants.

- Films resistance Parts of poly- Parts of mixed Parts of aldehyde -'Baking- 4 "Example-No. epoxide ester condensate schedule, w

m1n./ 0. Boiling water 5% aqueous N'aOH at-25C.

10.5 Epon 1001 5.0m. 1.5 Ex. XIX /1 1 hr 168 hrs; I 19.3 Epon 1004 5.0 Ex. 2 4 Ex. XIX 7 hrs. 30 111111.. 110 hrs. 7. 5.0 Ex. 2 5 Ex. XIX-.. 10 min 168 hrs. 2 5.0'Ex'. 2 7 Ex. XVIII. 7 hrs. 20 min 108 hrs. 2.5Ex. 2 3 Ex. XVIII 5.0 Ex. 1 3 Ex. XVIIL 5.0 Exl 1 6 Ex. XVIL 5.0 Ex; 1 1 .Ex.:XVII. 1.2 EDOH 864 5.0 Ex. 0.6 Ex. XVIL. 0.8 Epon 1001 5.0 Ex. 1.5 EX. VII 108 hrs 22.0 Epon 1004---- 5 0 Ex. vI 2.8 Ex. XVII 50/175 168 hrs 15.1 Epon 1004 5.0 Ex. IX 2.0 EX. XVII 168 hrs 22.2 Epon 1007.. 5.0 EX. 2.7 Ex.XvIII. 15s hrs 5.7 Epon 864 5.0 Ex. 1.1 Ex; XVIII 8- hrs.

0.5 Ex. I 8.0.Ex. XVIIL. 150 hrs 2.0 Ex. .0 Ex. XVIII 4 hrs. 5.0 Ex. .3 10min 5.0 Ex. .1 :15 min 5.0 Ex. .6 16 8-,hrs 5.0 EX. .2 10min 5.0 Ex. .6 5 hrs. 30 min 40min 5.0 Ex. .2, 7 hrs. 20 min 10 min 5.0 Ex. .3 4hrs 5 min. 5.0 Ex. .3 Ex. XVIII 30/175 1 hr.20'min 2.'hrs.'15 min. 5.0 Ex. 1.0 Ex. XVIII /200 3 hrs hrs. 5 o EX. 1.0 Ex. VII.

5 hrs 10 min. 5 0 Ex. 1.01m. XVII. 5 min.

. 1.0 Ex. 0.5 Ex. 2.0 Ex. 5.0 Ex. 5.0 Ex. 1.8 5.0 Ex. 5.7 5.0 Ex. 5.9 5.0 Ex. 12. 5.0 Ex. 6.6 5.0 Ex. 6.8 5.0 Ex. 10.0 5.0 Ex. 8.4 Ex. 5.0 Ex. 8.4 Ex. 5.0 Ex. 1.0 Ex. 8.0,Ex. 2.5 Ex. 2.5 Ex. 1.0 1.0 E. 6.6 Ex. 10.0 Ex. 8.7 Ex. EX. 6.8 Ex. 10.0 Ex. 9.1 EX. 1.0.0 Ex. 1.1 Ex. 10.0 Ex. 1.4 Ex. 10.0 Ex. 51 Ex. 10.0 Ex. 7.0 Ex. 10.0 Ex. 8.1 Ex. 10.0 Ex. ,7.6 EX. 10.0 Ex.

7.6 Ex. 10.0 Ex. 103E 10.0 Ex. 1.0 E. 1.0 Ex. 8.0 E 1.5 Ex. V1... 2.5 Ex. XV 2.5 E

tonxsxvrrr. 2111s. 10 min.

2 hrs. 15 min. 7 hrs.20'-mi.n

72 hrs. 7

2 hrs 15 min. 168'hrs.

8 hrs.

8 hrs.

5 hrs.

* 8 hrs.

1 hrs.

2 hrs. '10 min. 168 hrs.

it should be appreciated that while there are above disclosed but a limited number of embodiments of this invention, it is possible to produce still other embodiments without departing from the inventive concept herein disclosed.

It is claimed and desired to secure by Letters Patent:

1. A new composition of matter comprising the insoluble condensation product obtained by heating (A) an ester of a fusible polyhydric alcohol and a mixture of (1) a pent-anoic acid consisting essentially of 4,4--bis(4-hydroxyaryDpentanoic acid wherein the hydroxyaryl radical is a hydroxyphenyl radical and is free from substituents other than alkyl groups of from 1-5 carbon atoms and (2) at least one unsubstituted aliphatic hydrocarbon monocarboxylic acid having from about 10 to about 36 carbon atoms, (B) a polyepoxide containing an average of more than one oxirane group per molecule wherein said polyepoxide is composed of the elements carbon,

hydrogen and oxygen and having oxygen present only in the groups selected from the group consisting of OH, -C0O, ethereal oxygen and oxirane groups, and (C) a fusible phenol aldehyde condensation resin.

2. The composition of matter as described in claim 1 wherein the pentanoic acid of (A) consists essentially of .4,4 bis(4-hydroxyaryl)pentanoic acid wherein the hydroxyaryl radical is a hydroxyphenyl radical and is free from substituents other than alkyl groups of one carbon atom.

3. The composition of matter as described in claim 1 18 wherein the pentanoic acid of (A) is 4,.4-bis(4-hydroxyphenyl)pentanoic acid.

4. The composition of claim 3 wherein the aliphatic hydrocarbon monocarboxylic acid of (A-2) is at least one unsaturated aliphatic hydrocarbon monocarboxylic acid having from about 10 to about 36 carbon atoms.

5. The composition of matter of claim 3 wherein (B) I is a polyglycidyl ether of a member of the group consisting of polyhydric phenols and polyhydric alcohols.

6. The composition of matter as described in claim 3 wherein (B) is a polyepoxide polyester of tetrahydrophthalic acid and a glycol wherein the epoxy oxygen bridges adjacent carbon atoms on the tetrahydrophthalic acid residue.

7. The composition of matter as described in claim 3 wherein (B) is an aliphatic polyepoxide, said polyepoxide having only hydroxyl groups in addition to oxirane groups.

8. The composition of matter of claim 3 wherein (B) is an epoxidized acid from the group consisting of vegetable oil acid and fish oil acid.

9. The composition of matter of claim 3 wherein (C) is a hydroxybenzene-formaldehyde condensation resin.

10. The composition of matter of claim 3 wherein (C) is a p-tert-butylphenol-formaldehyde condensation resin.

11. The composition of matter of claim 3 wherein (C) is a bis-(p-hydroxyphenyl)isopropylidene-formaldehyde condensation resin.

No references cited. 

1. A NEW COMPOSITION OF MATTER COMPRISING THE INSOLUBLE CONDENSATION PRODUCT OBTAINED BY HEATING (A) AN ESTER OF A FUSIBLE POLYHYDRIC ALCOHOL AND A MIXTURE OF (1) A PENTANIOC ACID CONSISTING ESSENTIALLY OF 484-BIS(4HYDROXYARYL) PENTANIOC RADICAL AND IS FREE FROM SUBSTITCAL IS A HYDROXPHENYL RADICAL AND IS FREE FROM SUBSSTITUENTS OTHER THAN ALKYL GROUPS OF FROM 1-5 CARBON ATOMS AND (2) AT LEAST ONE UNSUBSTITUTED ALIPHATIC HYDROCARBON MONOCARBOXYLIC ACID HAVING FROM ABOUT 10 TO ABOUT 36 CARBON ATOMS, (B) A POLYEPOXIDE CONTAINING AN AVERAGE OF MORE THAN ONE OXIRANE GROUP PER MOLECULE WHEREIN SAID POLYPOXIDE IS COMPOSED OF THE ELEMENTS CARBON, HYDROGEN AND OXYGEN AND HAVING OXYGEN PRESENT ONLY IN THE GROUPS SELECTED FROM THE GROUP CONSISTING OF -OH, -COO-, ETHERAL OXYGEN AND OXIANE GROUPS, AND (C) A FUSIBLE PHENOL ALDEHYDE CONDENSATION RESIN. 